Lecture 1

Mixing vs Separation
 Two substances a and b will mix or separate depending on free enthalpy of mixing(ΔG )
m
ΔG = ΔH – TΔS
m m m
where ΔH is the enhalpy of mixing and ΔS is the entropy of mixing.

m m
 ΔG < 0:Spontaneous mixing ;

m
 ΔG > 0:Spontaneous separation

m
 In most cases and always when A and B are gases the mixing occurs spontaneously and
minimum amount of energy, W = ΔG
min m
 The actual energy requirement for the separation will bemany times greater than W
min
 The actual energy requirement depends on the type of separation processes
Membrane Separations
What is a membrane?
A membrane is a physical barrier (no necessarily solid) that gives, or at least helps, the separation
of the components in a mixture.
-Membrane processes are not based in thermodynamic equilibrium but based in the different
transport rate of each species through the membrane.
-The membrane market is still growing. In the 1986-96 decade, the sales related to membrane
products and systems doubled.
- In 1998, these sales were over 5000 million €.
Advantages
Energy savings. The energy consumption is very low as there is no phase change.
Low temperature operation. Almost all processes proceed at room temperature, thus they can
deal with compounds that are not resistant at high temperatures.
Recovery. Both the concentrate and the permeate could be recovered to use.
Water reuse. When applied to recover water, they avoid the transport of large water volumes
and permit the reduction of the Chemical Oxygen Demand (COD) loading in sewage plants.
Compact operation. Which permits to save space .
Easy scale-up. Because usually they are designed in modules, which can be easily connected.
Automatic operation. The most of the membrane plants are managed by expert systems.
Tailored systems. In many cases, the membranes and systems can be specifically designed
according the problem.
Disadvantages
High cost. Membranes (and associated systems) are costly, but for low selective separations.
Lack of selectivity. In many cases, the separation factors are still insufficient.
Low fluxes. The permeat flowrate available are still too low for some applications.
Sensitive to chemical attack. Many materials can be damaged by acids, oxidants or organic
solvents.
Lack of mechanical resistance. Many materials do not withstand abrasion, vibrations, high
temperatures or pressures.
- The membrane operations more widely used are those based in applying a pressure difference
between both sides of the membrane.
Micro Filtration (MF)

(10-0.1m)
Bacteria, suspended particles
Ultrafiltration(UF)
(0.05-0.005m)
Colloids, macromolecules
Nanofiltration (NF)
5e-3-5.e-4m
Sugars, dyes, divalentsalts
Reverse Osmosis(RO)
(1.e-4-1e-5 m)
Monovalent salts, ionic metals
Water
• Microfiltration (MF).
• Ultrafiltration (UF).
• Nanofiltration (NF).
• Reverse osmosis (RO).
- Although similar in appearance, the involved mechanisms in the separation can be very very
different.
Name of the membrane process as function of the particle size.

- There are other separation operations where a membrane is the responsible of the la selective
separation of the compounds:
• Dialysis. • Gas per eation (GP). • Electrodialysis (ED).
• Liquid membranes. • Pervaporation.
- In others, the membrane is not directly responsible for the separation but it actively participates
in:
• Membrane extraction.
• Membrane distillation.
• Osmotic distillation.
Type of filtration.
Simple scheme of a membrane module.
- Synthetic membranes are solid barriers that allow preferentially to pass specific compounds due
to some driving force.
(Very) Simple scheme for some mechanisms of selective separation on a porous membrane.
- The separation ability of a synthetic material depends on its physical, chemical properties.
• Pore size and structure
• Design
• Chemical characteristics
• Electrical charge
- The membranes can be roughly divided in two main groups: porous and non porous.
- Porous membranes give separation due to...
• size
• shape
• charge
...of the species.
- Non porous membranes give separation due to...
• selective adsorption
• diffusion
...of the species.
Main parameters.
- Rejection, R, if there is just one component (RO)
 CA,f  CA,p   C 
R(%)  100   100 1  A,p 
 CA,f   CA,f 
- Separation factor - Enrichment factor
CA,p/CB,p A CA,p
α A,B   A 
CA,f /CB,f B CA,f
for two or more component
Main parameters.
- In RO, often we use the Recovery (Y)
Qp
Y(%)  100
Qf
3
Q : Permeate flowrate (m /s)
p
3
Q : Feed flowrate (m /s)
f
Main parameters.
- Passive transport in membranes. The permeate flux is proportional to a given driving force
(some difference in a property).
Flux(J)  Constant(A)
Driving Force(X)
Driving forces:
 Pressure (total o partial)

 Concentration
 Electric Potential
Main parameters.
Membrane processes and driving force.
Feed phase Permeate phase Driving Force

Process
Microfiltration L L ΔP
Ultrafiltration L L ΔP
Nanofiltration L L ΔP
Reverse Osmosis L L ΔP
Dialysis L L Δc
Electrodialysis L L ΔΕ
Pervaporation L G ΔP
Gas Permeation G G ΔP
Main parameters.
- Permeate flux.
In MF and UF, porous membrane model is assumed, where the a stream freely flows through the
pore. Then, the transport law follows the Hagen-Poiseuille equation.
J w  Qw  r  P
2
A m 8 d
3 2 3 2
J : Solvent flux (m /s·m ) Q : Solvent flowrate (m /s) A : Membrane area (m )
w w m
d: Membrane thickness (m) : Viscosity (Pa ·s) P: Hydraulic pressure difference (Pa)
r: Pore radius (m) : Porosity : Tortuosity
Main parameters.
- The above model is good for cylindrical pores. However, if the membrane is rather formed by a
aggregated particles, then the Kozeny-Carman relation works much better.
3  P
J w  Qw 
A m KS 2 12 d
3 2 3
J : Solvent flux (m /s·m ) Q : Solvent flowrate (m /s)
W W
2 3
S: Particle surface area (m /m ) K: Kozeny-Carman constant
2
A : Membrane area (m ) d: Membrane thickness (m) : Viscosity (Pa ·s)
m
- In the operations governed by the pressure, a phenomenon called concentration polarisation
appears, which must be carefully controlled. This is due to the solute accumulation neighbouring
the membrane surface.
Formation of the polarisation layer.
- Concentration polarisation.
(It is not fouling!!!)
- Fouling: Irreversible reduction of the flux throughout the time.
• Pore size reduction by irreversible adsorption of compounds.
• Pore plugging.
• Formation of a gel layer over t e membrane surface (cake).
- Membrane can be classified in several ways, but always there are arbitrary classifications.
• Structure: symmetric, asymmetric
• Configuration: flat, tubular, hollow fiber
• Material: organic, inorganic
• Surface charge: positive, negative, neutral
• ...and even other divisions and subdivisions
- Structure:
•Symmetric. Also called homogeneous. A cross section shows a uniform porous structure.
•Asymmetric. In a cross section, one can see two different structures, a thin dense layer and
below a porous support layer.
-Integral: the layers are continuous.
-Composites: the active layer (thickness 0.1-0.5 μm) is supported over a highly porous layer (50-
150 μm), sometimes both layers are of different materials.
Symmetric UF membrane of 0.45 m made of cellulose acetate (Millipore).
Surface Cross section
TM
Symmetric ceramic membrane of 0.2 m made of alumina (Al O ) (Anopore ).
2 3
Asymmetric ceramic membrane made of -Al O (Membralox).
2 3
UF integral asymmetric membrane made of polypropylene.
RO composite membranes.
- Configuration and modules
• Configuration: geometric form given to the synthetic membranes.
• Module: name of the devices supporting one or several membranes (housing).
The module seals and isolates the different streams. The geometry and specific fluid movement
through the confined space characterises each module. The type of flux, the transport mechanism
and the membrane surface phenomena depend on the module design.
- Configuration:
• Flat.
- The active layer is a flat.
- Synthesised as a continuous layer.
- Later, one can select a desired geometry (rectangle, circle,...) to be placed in the module.
- Used in two kind of modules: plate-and-frame and spiral wound.
- High surface area/volume ratio.
Plate-and-Frame Membrane System.

Consists of layers of membranes separated by corrugated structural sheets, alternating layers with
feed material f owing in and retentate flowing out in one direction, while permeate flows out in
the other direction.
Spiral-wound module.
Spiral-wound module.
- Configuration:
• Tubular.
- It is like a tube.
- Usually the active layer is inside.
- The permeate crosses the membrane layer to the outside (this is, the feed flows inside).
- Low surface are/volume ratio.
- Several lengths and diameter (>10 mm).
- Modules grouping one or various membranes.
Different types of tubular modules.
Hollow fiber module.
Cross section of hollow fiber (Monsanto). Comparison with a clip.
Hollow fiber cross section of polyamide for RO (DuPont).
Hollow fiber made of polysulfone (  1 mm) for UF (detail).
Hollow fiber cross section of   1 mm (Monsanto).
Hollow fiber surface of polypropylene (Celgard).
- Comparison between modular configurations.
Module
Parameter Tubular Spiral-wound Hollow fiber
Specific surface area (m2/m3) 300 1000 15000
Inside diameter or spread (mm) 20-50 4-20 0.5-2
Flux (L/m2 day) 300-1000 300-1000 30-100
Production (m3/m3 per module & day) 100-1000 300-1000 450-1500
Space velocity (cm/s) 100-500 25-50 0.5
Pressure loss (bar) 2-3 1-2 0.3
Pretreatment Simple Medium High
Plugging Small Medium Elevated
Replacement Easy Difficult Impossible
Cleaning:
Mechanical Possible Not possible Not possible
Chemical Possible Possible Possible
- Comparison between modular configurations.
Modular configurations and processes.
Module
Operation Tubular Spiral-wound Hollow fiber
Reverse Osmosis A VA VA
Ultrafiltration VA A NA
Microfiltration VA NA NA
Pervaporation A VA VA
Gas Permeation NA VA VA
VA = Very appropriate; A = Appropriate; NA = Not appropriate
- Material:
• Organic.
- Made of polymers or polymer blends.
- Low cost.
- Problems with their mechanical, chemical resistance.
Temperature
pH, Solvents
Pressure
Polypropylene with 0.2 m pores (Accurel).
Polytetrafluoroetylene with 0.2 m pores.
Membrane Technology
• Dialysis
- Applied since the 70’s.
- Low industrial interest.
- Ions & species of low MW (<100 Da).
- Ionic Membranes (just like ED).
- Driving Force: concentration gradient.

- Slow and low selective.
Membrane Technology
• Dialysis
- Artificial kidney.
- NaOH recovery in textile effluents, alcohol removal from beer, salts removal (pharmaceutical
industry).
Membrane Technology
• Dialysis
Looks not very important...?.
PV
GS ED
HD MF
UF
RO
Membrane and mod le markets
Membrane Technology
• Electrodialysis (ED)
- First applications back at 30’s.
- Ion Separations.
- Ionic Membranes (non porous).

- Driving Force: gradient in electrical potential.
- Potential: 1-2 V.
- Flat configuration.
- Hundreds of anionic and cationic membranes placed alternatively.
- Orthogonal electrical field.
Membrane Technology
Membrane Technology
Membrane Technology
- Ionic Membranes (non porous).
- Based n polystyrene or polypropylene with sulfonic and quaternary amine groups.
- Thickness: 0.15-0.6 mm.
- ED with reverse polarization (EDR).
- ED at high temperature (60ºC).
- ED with electrolysis.
Membrane Technology
- Required membrane area
 Mass balance (in equivalents)
Vc
C out
               j
j  dA V Cz  dc  0

m
Vc
c in
2
 Charge flow i: electric current density (A/m )
2
Am: membrane surface (m )
j   F i  dI combining

 dAm
AT  N  Am 

N VC  c in  cout

zF


V  cin  cout

zF
 i  i
2
η: global electrical efficiency (~0.5 commercial equipment) j: cation flow (eq/m s)
F: Faraday constant (96500 C/eq)
N: number cells in the equipment
z: cation charge (eq/mol)
Membrane Technology
- Then the required energy, E (J), is

E  N UC  I  t  NI 2R  t
C UC: potential gradient in a cell (V)
RC: total resistance in a cell ()
as
I  i  Am 
 

VC  cin  cout zF

then
 V c  z  F   V c  z  F 
2 2
EN  C  R C t ó P  N  C   RC
     
P: required Power (J/s)
Membrane Technology
3
Where, the required specific energy, (J/m ), is
 c  z  F 
2
E
Ê   VC   R C
NVC t   
La cell resistance can be estimated from a model based on series of resistances where the
resistances to transport are considered through two membranes and the compartments
concentrate and diluted.
Membrane Technology
- How to determine perational i?
 Cation Transport
i  z c D c 
 i 
 tM  D t
DM
F  F
D F  z  cD  c 

i
DM
 t M  t  
+
If c =0
DM
D F  z  c
ilim D  
 t M  t 
Usually: i = 0.8i
lim
t: transport number
D: diffusion coefficient
Membrane Technology
- Intensity Evolution versus applied potential
Membrane Technology
- Fields of application:
Water desalination.
- Competing to RO.
- Econo ically more interesting at very high or very salt concentrations.
- Other fields of application:
Food Industry.
Treatment of heavy metal polluted water.
Membrane Technology
- Examples:
 Production of drinking water from salty water.
 Water softening.
 Nitrate removal.
 Lactose demineralization.
 Acid removal in fruit juice.
 Tartrate removal from wines.
 Heavy metal recovery.
 Production of chlorine and sodium hydroxide.
Membrane Technology
electrolytic Cell for the production of chlorine and sodium hydroxide with cationic
membrane.
Membrane Technology
Electrolytic cell for the production of sulfuric acid and sodium hydroxide with bipolar
membrane.
Membrane Technology
Hydrogen fuel cell with a cationic membrane.

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Mixing vs Separation

where ΔH is the enhalpy of mixing and ΔS is the entropy of mixing.

 ΔG < 0:Spontaneous mixing ;

 ΔG > 0:Spontaneous separation

 The actual energy requirement depends on the type of separation processes

- In 1998, these sales were over 5000 million €.

Compact operation. Which permits to save space .

Micro Filtration (MF)

• Reverse osmosis (RO).

Name of the membrane process as function of the particle size.

• Dialysis. • Gas per eation (GP). • Electrodialysis (ED).

• Liquid membranes. • Pervaporation.

Simple scheme of a membrane module.

• Pore size and structure

...of the species.

- Non porous membranes give separation due to...

...of the species.

- Rejection, R, if there is just one component (RO)

- Separation factor - Enrichment factor

- In RO, often we use the Recovery (Y)

 Pressure (total o partial)

Membrane processes and driving force.

Feed phase Permeate phase Driving Force

r: Pore radius (m) : Porosity : Tortuosity

Formation of the polarisation layer.

(It is not fouling!!!)

• Formation of a gel layer over t e membrane surface (cake).

• Structure: symmetric, asymmetric

• Configuration: flat, tubular, hollow fiber

• Material: organic, inorganic

• Surface charge: positive, negative, neutral

• ...and even other divisions and subdivisions

-Integral: the layers are continuous.

Surface Cross section

UF integral asymmetric membrane made of polypropylene.

- Configuration and modules

• Configuration: geometric form given to the synthetic membranes.

• Module: name of the devices supporting one or several membranes (housing).

- Synthesised as a continuous layer.

- Used in two kind of modules: plate-and-frame and spiral wound.

- High surface area/volume ratio.

Plate-and-Frame Membrane System.

- Usually the active layer is inside.

- Low surface are/volume ratio.

- Several lengths and diameter (>10 mm).

- Modules grouping one or various membranes.

Different types of tubular modules.

Cross section of hollow fiber (Monsanto). Comparison with a clip.

Hollow fiber made of polysulfone (  1 mm) for UF (detail).

Hollow fiber surface of polypropylene (Celgard).

Parameter Tubular Spiral-wound Hollow fiber

Specific surface area (m2/m3) 300 1000 15000

Inside diameter or spread (mm) 20-50 4-20 0.5-2

Flux (L/m2 day) 300-1000 300-1000 30-100

Production (m3/m3 per module & day) 100-1000 300-1000 450-1500

Space velocity (cm/s) 100-500 25-50 0.5

Pressure loss (bar) 2-3 1-2 0.3

Pretreatment Simple Medium High

Plugging Small Medium Elevated

Replacement Easy Difficult Impossible

Mechanical Possible Not possible Not possible

Chemical Possible Possible Possible

Operation Tubular Spiral-wound Hollow fiber