Pressure Driven Processes

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
- Pressure-driven membrane processes:

Microfiltration (MF)
Ultrafiltration (UF)
Nanofiltration (NF)
Reverse Osmosis (RO)
- 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.
- 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
- 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
- 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.
- 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*.
- Moderate operating pressure: 1 to 10 bar.
- Typical flux: 5-200 L m-2 h-1.
* 1 Dalton 1.6610-24 g
- 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.
- 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.
- 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.
- 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.
- 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.
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.
- Moderate Pressure: 15 bar.
- Typical flux: 20-80 L m-2 h-1.
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.
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).
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).
- Operating pressure between 10-25 (brackish) and
40-80 bar (seawater).
- Average flux: 5-40 L m-2 h-1.

(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

- 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

- 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)

- 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 )

- 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.

- 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

- 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).
ED
5%
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
Feed
UF
pretreatment
Permeate
1st pressure stage

: RO module
2nd pressure stage
Concentrate
Water production plant based on RO.

Pressure Driven Processes

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Membrane Separations

- Pressure-driven membrane processes:

Low molecular substances,

High molecular substances, viruses

- Pressure-driven membrane processes:

Continuous UF process for recovering of lactoserum.

- Still looking for applications. Potentially when

Reverse Osmosis (RO) [Hyperfiltration]

Reverse Osmosis (RO)

Reverse Osmosis (RO)

- Why does water cross the membrane ?

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

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

Reverse Osmosis (RO)

Reverse Osmosis (RO)

t: temperature; c: compaction; e: fouling

Reverse Osmosis (RO)

Js: Solute mass flux (mol/sm2)

Reverse Osmosis (RO)

Reverse Osmosis (RO)

Reverse Osmosis (RO)

D: Diffusion coeficient (m2/s)

Reverse Osmosis (RO)

Reverse Osmosis (RO)

Reverse Osmosis (RO)

1st pressure stage

2nd pressure stage

Water production plant based on RO.

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