Introduction to Membrane

Technology
Membrane Separations

What is a membrane?

? ? ?
A membrane is...
...a physical barrier (not necessarily solid)
that gives, or at least helps, the separation
of the components in a mixture.
Membrane Separations

The sorting demon...

Membrane Separations

- Membrane processes are not based on

thermodynamic equilibrium but based on 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 €.

Membrane Separations
Membrane Separations

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.
Membrane Separations

Advantages
 Compact operation. Which permits to save space .

 Easy scale-up. Because usually they are designed in

modules, which can be easily connected.

 Automatic operation. 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.
Membrane Separations

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.
Membrane Separations

- The membrane operations more widely used are

those based in applying a pressure difference
between both sides of the membrane.
• Microfiltration (MF). Micro Filtration (MF)
(10-0.1m)
Bacteria, suspended particles

• Ultrafiltration (UF). Ultrafiltration (UF)

(0.05-0.005m)
Colloids, macromolecules

• Nanofiltration (NF). Nanofiltration (NF)

5e-3-5.e-4 m
Sugars, dyes, divalent salts
Reverse Osmosis (RO)

• Reverse osmosis (RO).

(1.e-4-1e-5 m)
Monovalent salts, ionic metals

Water

- Although similar in appearance, the involved

mechanisms in the separation can be very very
different.
Membrane Separations

Na+ Hemoglobin Pseudomonas Starch

(0,4 nm) (7 nm) Diminuta (10000 nm)
(280 nm)
H2O Glucose Influenza Virus Staphylococcus
(0,2 nm) (1 nm) (100 nm) (1000 nm)

Salts and Microfiltration

low molecular
weight Ultrafiltration
compounds Cells,
bacteria
Nanofiltration and
Virus and Emulsions
Vitamins proteins and colloids polymers
Reverse Osmosis
and sugars

0.1 1 10 100 1000 10000

Pore diameter (nm)

Name of the membrane process and function

of the particle size.
Membrane Separations

More examples.
Membrane Separations

... and more.

Membrane Separations

- There are other separation operations where

membrane is responsible for the selective
separation of the compounds:
• Dialysis. • Gas permeation (GP).
• Electrodialysis (ED).
• Liquid membranes.
• Pervaporation.

- In others, the membrane is not directly

responsible for the separation but it actively
participates:
• Membrane extraction.
• Membrane distillation.
• Osmotic distillation.
Membrane Separations

Dead-end Cross-flow

Type of filtration.
Membrane Separations

CA,f, CB,f CA,r, CB,r

Feed Retentate
Membrane
(Concentrate)

Permeate
CA,p, CB,p
(Filtrate)

Simple scheme of a membrane module.

Membrane Separations

- 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.
Membrane Separations

- The separation ability of a synthetic material

depends on its physical, chemical properties.

• Pore size and structure

• Design
• Chemical characteristics
• Electrical charge
Membrane Separations

- 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.
Membrane Separations

Main parameters.
- Rejection, R, if there is just one component (RO)
 CA,f  CA, p   CA, p 
R (%)  100     100  1 
 


 C A,f   C A,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
Membrane Separations

Main parameters.

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

Qp
Y(%)   100
Qf

Qp: Permeate flowrate (m3/s)

Qf: Feed flowrate (m3/s)
Membrane Separations

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
Membrane Separations

Main parameters.
Membrane processes and driving force.
Feed Permeate Driving
Process phase phase Force
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
Membrane Separations

Main parameters.
- Permeate flux.
In MF and UF, porous membrane model is assumed, where
the stream freely flows through the pore. Then, the
transport law follows the Hagen-Poiseuille equation.
Q
Jw  w    r 2 P

A m 8   d
Jw: Solvent flux (m3/s·m2)
Qw: Solvent flowrate (m3/s)
Am: Membrane area (m2) r: Pore radius (m)
d: Membrane thickness (m) : Porosity
: Viscosity (Pa ·s) : Tortuosity
P: Hydraulic pressure difference (Pa)
Membrane Separations

Main parameters.
- The above model is good for cylindrical pores.
However, if the membrane is rather formed by
aggregated particles, then the Kozeny-Carman relation
works much better.

Jw  Q w   3
 P
A m K   S2  1 2 d
JW: Solvent flux (m3/s·m2)
QW: Solvent flowrate (m3/s)
S: Particle surface area (m2/m3)
K: Kozeny-Carman constant d: Membrane thickness (m)
Am: Membrane area (m2) : Viscosity (Pa ·s)
Membrane Separations

- 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.
Permeate
membrane
Feed
Polarisation layer

membrane
Permeate

Formation of the polarisation layer.

Membrane Separations

- Concentration polarisation.

(It is not fouling!!!)

Membrane Separations

- 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

the membrane surface (cake).
Membrane Separations

- 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
Membrane Separations

- 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.
Membrane Separations

Symmetric UF membrane of 0.45 m made of

cellulose acetate (Millipore).
Membrane Separations

Surface Cross section

Symmetric ceramic membrane of 0.2 m made of

alumina (Al2O3) (AnoporeTM).
Membrane Separations

Asymmetric ceramic membrane made

of -Al2O3 (Membralox).
Membrane Separations

UF integral asymmetric membrane made of

polypropylene.
Membrane Separations

Cellulose acetate

Polyamide

RO composite membranes.
Membrane Separations

- 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.
Membrane Separations

- 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.
Membrane Separations

Plate-and-Frame Membrane System.

Consists of layers of membranes separated by corrugated
structural sheets, alternating layers with feed material
flowing in and retentate flowing out in one direction,
while permeate flows out in the other direction.
Membrane Separations

Spiral-wound module.
Membrane Separations

Spiral-wound module.
Membrane Separations

- 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.
Membrane Separations

Different types of tubular modules.

Membrane Separations

Hollow fiber module.

Membrane Separations

Hank of polyamide hollow fiber for RO (DuPont).

Membrane Separations

Cross section of hollow fiber (Monsanto).

Comparison with a clip.
Membrane Separations

Hollow fiber cross section of polyamide

for RO (DuPont).
Membrane Separations

Hollow fiber made of polysulfone

(  1 mm) for UF (detail).
Membrane Separations

Hollow fiber cross section of   1 mm

(Monsanto).
Membrane Separations

Hollow fiber surface of polypropylene (Celgard).

Membrane Separations

Hollow fiber ceramic membranes (CEPAration).

Membrane Separations

- 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
 Membrane Separations

- 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
Membrane Separations

- Material:

• Organic.

- Made of polymers or polymer blends.

- Low cost.
- Problems with their mechanical, chemical
resistance.
Temperature
pH, Solvents
Pressure
Membrane Separations

Polypropylene with 0.2 m pores (Accurel).

Membrane Separations

Polytetrafluoroetylene with 0.2 m pores.

Membrane Separations

Polytetrafluoroetylene with 0.2 m pores.

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.
Membrane Technology

• Electrodialysis (ED)
Membrane Technology

• Electrodialysis (ED)
Membrane Technology

• Electrodialysis (ED)
- Ionic Membranes (non porous).
- Based on polystyrene or polypropylene with
sulfonic and quaternary amine groups.
- Thickness: 0.15-0.6 mm.
Membrane Technology

• Electrodialysis (ED)
- Fields of application:
Water desalination.
- Competing to RO.
- Economically more interesting at very high or
very salt concentrations.

- Other fields of application:

Food Industry.
Treatment of heavy metal polluted water.
Membrane Technology

• Electrodialysis (ED)
- 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

• Electrodialysis (ED)

electrolytic Cell for the production of chlorine and

sodium hydroxide with cationic membrane.
Membrane Technology

• Electrodialysis (ED)

Electrolytic cell for the production of sulfuric acid

and sodium hydroxide with bipolar membrane.
Membrane Technology

• Pervaporation

- Discovered 1917.
- Only operation with phase change.
- Non-Porous Membranes.

- Mechanism solution-diffusion.

- Driving force: difference in partial pressure.

-Vacuum (<40 mm Hg), dilution (inert gas, N2)

or temperature difference.
Membrane Technology

• Pervaporation

Retentate
Pervaporat.
module
Feed

Condenser
Heater

Permeate
Vacuum
condensate
pump

General Pervaporation system.

Membrane Technology

• Pervaporation
- Industrial applications.
- Alternative to distillation when thermodynamic
limitations.
 Low energy costs.
 Low investment costs.
 Better selectivity, without
thermodynamic limitations.
 Clean and closed operation.
 No process wastes.
 Compact and scalable units.
Membrane Technology

• Pervaporation
- Drawbacks:
 Scarce Membrane market.
 Low permeate flows.
 Limited applications:
- Organic substances dehydratation.
- Recovery of volatile compounds at low
concentrations.
- Separation of azeotropic mixtures.
Membrane Technology

• Pervaporation.

- Do not mistake with a membrane distillation where a

membrane is just separating phases.

- Three steps mechanisms:

 Selective absorption on the membrane.

 Dissolution at the membrane.
 Diffusion through the membrane.
 Membrane Technology

• Pervaporation
- The membrane is active in this process.
- The permeability coefficient (P) of a compound
depends on the solubility (S) and the diffusivity (D),
in the polymeric phase, of the crossing compound
Pi = Si (ci, cj)· Di (ci, cj)
- Simplificated transport equation:
Pi

Ji   x i   i  pio  yi  pp
d

Ji: flux of component i d: membrane thickness xi: molarfraction in liquid i: activity coefficient
pio: vapour pressure yi: molar fraction at permeate pp: pressure at permeate side
Membrane Technology

• Pervaporation

- Main membrane parameters:

- Separation factors - Enrichment factors

CA,p /CB,p A CA,p
α A,B   A 
CA,f /CB,f B CA,f
 Membrane Technology

• Pervaporation
Condenser
Distillation
column
Ethanol >90% w/w

Feed Intermediat Ethanol >99.95% w/w

tank

Permeate

Pervap. unit
oduction
om Ethanol 20-80% Ethanol 15% w/w
w/w Boiler
niville,
Water

Combination of distillation and pervaporation for

the production of pure ethanol.
Membrane Technology

• Pervaporation
Dehydration of organic solvents.

Organic solvents to apply pervaporation.

Methanol Alil alcohol Ethyl Acetate Tricloretilene

Ethanol Furfurol Buthyl acetate Tetrachloretane
n-Propanol Methylfurfurol Diethyl ether Tretrahydrofurane
Isopropanol Diethilenglicol Diisopropyl ether Aniline
n-Buthanol Acetone Dipropyl ether Benzene
t-Buthanol Buthanone Ethyl propyl ether Toluene
2-Penthanol Cyclohexanone Chloroform Xylene
Hexanol Methyl ethyl Ketone Methyl Chloride Ethylen diamine
Cyclohexanol Metil isobuthyl Ketone Chlorethylene Ethanol amine
Isoamilic Alcohol Caprolactame Dichloro ethylene Diethyl amine

 Hydrophilic membranes: PVA, PAN...

Membrane Technology

• Pervaporation
- Organic compounds recovery.
 For volatile compounds.
 Economically competitive.
 Hydrophobic membranes: PDMS and
derivatives.
- Azeotrope breaking of organic compounds.
 Studied at lab scale.
 Low selectivity.
Membrane Technology

• Pervaporation

Lab scale separations reported.

Mixture Membrane Selectivity

Ethylbenzene/xylene Polyethylene Not available
p-xilene/o-xilene Polyethylene Not available
m-xilene/p-xilene Polypropilene m-Xylene
Dichlor ethane/trichlor Poliamide/polyeth Dichlorethane
ethane
Benzene/cyclohexane Polyimide Benzene
Acetone/cyclohexane Polyimide Acetone
Membrane Technology

• Pervaporation
Pure cyclohexane

Solvent
Pervaporation
C unit C
o o
l Pure benzene
l
u u
m m
Feed n n

1 2

Hybrid process: extractive distillation and pervaporation

for the production of pure benzene and cyclohexane .
Membrane Technology

• Gas permeation
- Since 50’s.
- Membranes: porous and no porous.
- Several possible mechanisms for gas transport:
X Viscous Flow.
 Knudsen Flow.
 Solution-diffusion.

- The last two are selective.

Membrane Technology

• Gas Permeation
- Knudsen Flow (porous membranes). When the
porous diameter is on the range of the average free
space of the molecule (kinetic theory for gases).
 Dk
Ji    Pi Transport equation
d R T
2 8 R T
Dk   r  Knudsen diffusivity
3 M
Enrichment : porosity d: membrane thickness
: tortuosity R: gas constant
Ji Mj
 T: temperature P: transmembrane P
Jj Mi r: porus radi
M: MW
Membrane Technology

• Gas permeation
-Solution-diffusion (non-porous membranes).
Pi = Si· Di
The selectivity is referred to the separation factors of the
compounds to be separated

Pi  Di   Si 
ij   
Pj  D j   S j 
 
There are “slow” and “fast gases” for a determined membrane.
Membrane Technology

• Gas permeation

- Driving force: partial pressure gradient.

- Working pressure: up to 100 bar.
- Non-porous polymeric membranes:
PDMS, CA, PS, PES i PI
- Ceramic Membranes (small pores for Knudsen).

- Metallic membranes (Pd and Ag alloys).

Membrane Technology

• Gas permeation
- Asymmetric membranes.
- Thin polymer on a structural porous material.
- Preferred configuration Hollow Fiber or Spiral,
others like flat or tubular also possible.

- Applied in petrochemistry.
 Purification of H2, CO2, CH4 and gaseous
hydrocarbons of difficult distillation.
 Nitrogen purification.
Membrane Technology

• Gas permeation
- Some examples:
 Enrichment, recovery and dehydration of N2.
 H2 recovery in residual flows of proceses, purge or
natural gas.
 Adjust of the ratio H2/CO synthesis gas.
 Acid gas removal (CO2, H2S) from natural gas.
 Helium recovery from natural gas and other
sources.
 VOC removal from process flow.
Membrane Technology

• Gas permeation

H2 (96%) Gas to fuel-gas

permeation

Recycle

Hydrogen
Unitat de
isomerització
n-Butane Residuals gases

Isobutane Recycle of n-C4

Hydrogen recovery in a butane isomeration A typical PRISM®

Separator (Airproducts)
plant.
Membrane Technology

• Liquid Membranes

- A liquid barrier between two phases.

- Not yet industrial uses.

- Driving force: chemical potential, concentration.
- Two configurations:
 Emulsion (ELM).
 Supported Liquid Membranes (SLM).
Membrane Technology

• Liquid Membranes
Organic liquid + surfactant (membrane)
Possible
configuration
for LM.
Aqueous phase

Emulsion liquid Mem.

Receiving phase

Porous Organic liquid impregnated

Support into the pores
SLM
Membrane Technology

• Liquid Membranes
- Advantages:
 High flows due to the transport velocity in liquids.
 Selective separations due to the presence of specific reagents.

 Small quantities of solvent lets to the application of expensive

solvents.

- Drawbacks:
 Low stability of emulsions in ELM.
 Leaching out of organic phase from the pores of a SLM .
Membrane Technology
O

• Liquid Membranes O

O
Ag+
O

O
O

M + B MB
Ag+
M: selectively separated O
O
O
B: selective carrier
O O diphenyl-18-crown-6
O

N
MB
M M

O B
P

Liquid Membrane

Facilitated Transport in Liquid Membrane.

Membrane Technology

• Liquid Membranes
- ELM: low practical interest
- SLM: lab scale and few applications

- Hydrophobic Membranes (PE, PP ...).

- Hollow fibers.
- Potential applications:
 Selective removal and concentration of cations in solution.
 Selective separation of gases.
 Recovery of acid or basic compounds.
 Organic compound separation in complex mixtures.
Membrane Technology

• Other Techniques
- Membrane distillation.
 A hydrophobic membrane separates two aqueous
phases.
 The volatile compounds cross the membrane and
condensate.
 The hydrophobic membrane avoids the aqueous
phases to get into the membrane.
 The driving force in the temperature gradient.
Membrane Technology

• Other techniques
- Membrane distillation.
 Driven by the phase equilibrium in both sides of
the membrane.
 The membrane acts just like a physical barrier.
 Some applications:
 Water demineralization.
 Inorganic acid or salt concentration.

 Ethanol extraction at the fermentation.

Membrane Technology

• Other techniques
- Osmotic distillation.
 Similar to membrane distillation.
 Both phases at the same temperature.
 The partial pressure gradient due to the osmotic
pressure is the driving force.

 The osmotic pressure is risen by adding

appropriate compounds to the receiving phase.
 Attractive to the food industry provided it
maintains the temperature.
 Alcohol removal from wine and beer.
 Fruit juice enrichment.