Recall

• Introduction
• Classification of Membrane
• Membrane Material
• Classification of Membrane Processes

• Gasdiffusion in poroussolid
• Liquid permeation or dialysis
• Gaspermeation in amembrane
• Pervaporation

Types of Equipment (Membrane modules)

• Reverse osmosis(RO)
• Nano filtration membrane process(NF)
• Ultra filtration membrane process(UF)
• Micro filtration membrane process(MF)
 Gaspermeation in amembrane
• Types of flow in gas permeation:
– Assumptions: Isothermal conditions; negligible pressure drop in the
feed stream and permeate stream, permeability (PM) of each gas
component is constant
 Gas permeation in a Membrane:
Complete-mixing model for gas separation by membranes
 Gas permeation in a Membrane:
Complete-mixing model for gas separation by membranes
 Gas permeation in a Membrane:
Complete-mixing model for gas separation by membranes
 Gas permeation in a Membrane:
Complete-mixing model for gas separation by membranes
 Gas permeation in a Membrane:
Complete-mixing model for gas separation by membranes
 Gas permeation in a Membrane:
Complete-mixing model for gas separation by membranes
 Pervaporation
Pervaporation: Is a separation of liquid mixtures by partial
vaporization through a non-porous selectively permeable
membrane. A phase change occurs when the permeate changes
from liquid to vapor during its transport through the membrane. A
gradient in the chemical potential of the substance on the feed side
and the permeate side is the driving force for the process.
(Separation mainly due to polarity difference not on volatility
difference. Liquid mixture is in direct contact with one side of
membrane and where the permeate stream is removed in vapor
state from the other side of the membrane. Because of the presence
of the membrane, the liquid vapor equilibrium is perturbed
 Pervaporation

• Application: Separation of azeotropic mixtures (close boiling point component), heat sensitive products
Types of Equipment (membrane modules)

• Flat membrane/Plate and frame membrane

• Spiral wound membrane
• Tubular membrane, based on polymers
• Tubular membrane, based on ceramics
• Hollow-fiber membrane
 Plate and Frame Modules
Mainly used in experiments to characterize the permeability of the
membrane (PM)

Advantages:
1. Low hold up volume
2. Permeate from individual membrane element
3. Easy to fabricate and use, membrane replacement easy
4. Area of the membrane are well defined

Disadvantages:
1. Difficult to clean
2. Susceptible to plugging
3. High cost
 Plate and Frame Modules
• In some cases modules are stacked
together like a multilayers sandwich or
plate and frame filter press
 Spiral Wound Membrane
• Retain the simplicity of the flat membranes while increasing markedly the
membrane area per unit separator volume up to328 m2/m3 and decreasing
pressure drops.

Advantages:
1. Compact
2. Minimum energy consumption
3. Low capacity/operating cost

Disadvantages:
1. Not suitable for very viscous fluid
2. Dead spaces
3. Difficult to clean
4. Faulty membrane-Change whole module
 Spiral Wound Membrane
• The assembly consists of a sandwich of 4 sheets wrapped
around a central core of a perforated collecting tube.
• The whole spiral-wound element is located inside a metal
shell.
 Spiral Wound
• Used in plate-and-frame modules can be circular, square, or rectangle in
cross-section. The sheets are separated by support plates that channel the
permeate. Flat sheets can also be fabricated into spiral-wound modules.
The simplest design is the single-leaf spiral wound module.
 Hollow fiber membranes
• An alternative to the flat sheet membranes is the hollow-fibre membranes.
The diameter of hollow fibers varies over a wide range from 50 to 3,000
micrometer.
 Hollow fiber membranes
• The membranes are in the
shape of very-small diameter
hollow fibers. The inside
diameter of the fibers is in the
range of 100-500μm and the
outside 200-1000 μm, with
the length up to 3-5m.

• Thousands of fine tubes are

bound together at each end
into a tube sheet that is
surrounded by a metal shell
having a diameter of 0.1–0.2
m, so that the membrane
area per unit volume is up to
10000 m2/m3
 Hollow fiber membranes
Advantages:
1.Low hold up volume
2.Back flushing possible
3.Low energy consumption

Disadvantages:
1.Not suitable for viscous fluids
2.Single fiber damage-replace entire module
 Tubular Membrane
• These modules are now generally limited to ultrafiltration
applications, for which the benefit of resistance to membrane fouling
outweighs the high cost.
• Tubular membranes contains as many as 5 to 7 smaller tubes, each
0.5 to 1.0 cm in diameter, nested inside a single larger tube. In a
typical tubular membrane system, a large number of tubes are
manifold in series.
• The permeate is removed from each tube and sent to a permeate
collection header.

Advantages:
1. Easy to clean

Disadvantages:
1.High energy consumption
2.High hold up volume
Module CostEstimation
Some Membrane module Applications
 Recall
A driving force can make the mass transfer through the membrane possible;
usually, the driving force can be a pressure difference (∆P), a concentration
difference (∆c), an electrical potential difference (∆E).
Membranes can be classified according their driving forces:

∆P ∆c ∆T ∆E
Microfiltration Pervaporation Thermo-osmosis Electrodialysis
Ultrafiltration Gas separation Membrane Electro-osmosis
distillation
Nanofiltration Vapour Membrane
permeation electrolysis
Reverse Dialysis
osmosis
Piezodialysis Diffusion dialysis
 Pressure driven processes
High molecular substances, viruses
MF UF NF RO
∆P= 10-300 kPa 50-500 kPa 0.5-1.5 MPa 0.5-1.5 MPa

Bacteria, parasites, particles Mid-size organic substances,

multiple charged ions
Low molecular substances, single charged ions
 Reverse Osmosis
• Osmosis:
A spontaneous transport of solvent occurs from dilute solute or salt solution
to a concentrated solute or salt solution across a semipermeable
membrane which allows passage of the solvent but impedes passage of
the salt solutes.

Levels of both liquids are the same

 Reverse Osmosis
• Osmotic Equilibrium:
Solvent flow can be reduced by exerting a pressure on the salt-
solution side and membrane, until at certain pressure (Osmotic
pressure π) equilibrium is reached and the amount of solvent
passing in opposite direction is equal.

Rise in volume to equilibrate the osmotic pressure

 Reverse Osmosis
• Reverse osmosis
If pressure greater than the osmotic pressure is
applied, the direction of the water flow through the
membrane can be reversed
Reverse Osmosis
 for dilute water solutions

where n is the number of kg mol of solute,

Vm the volume of pure solvent water in m3 associated with n kg mol of solute,
R the gas law constant 82.057 x 10-3 m3atm/kg mol· K,
and T is temperature in K.
 Membrane characterization
• Membranes
• porous macropore >50nm
mesopore 2nm<<50nm
micropore <2nm
• nonporous  = pore diameter

Process Driving force Membrane Pore Separation principle

Microfiltration pressure difference macropore filtration
(0.1 - 1 bar)
Ultrafiltration pressure difference mesopore filtration
(0.5 – 10 bar)
Nanofiltration pressure difference micropore filtration/
(5 – 20 bar) electrostatic interaction/
solution-diffusion
Microfiltration
 Microfiltration
• Microfiltration is based on the restricted diffusion of
species through pores: Larger species or particles
are restricted from entering pores of 0.1 to 1
micron in size.
 Pores and pore geometries

Porous MF membranes consist of polymeric matrix in which

pores are present.
The existence of different pore geometries implies that
different mathematical models have been developed to
describe transport phenomena.
 Transport equations
• The Hagen-Poiseuille and the Kozeny-Carman equations can be applied to
demonstrate the flow of water through membranes. The use of these
equations depends on the shapes and sizes of the pores.

1. Hagen-Poiseuille

J – the solvent flux

  d P 2
P – pressure difference
J
32 x
x – thickness of membrane cylindrical pores
 tortuosity
  viscosity
d – the pore diameter ε –
surface porosity
 Transport equations
2. Kozeny-Carman

J
 3
P

KS 2 x closely packed spheres

S – surface area per unit volume

K – Kozeny-Carman constant
(depends on the pore geometry)
 Fouling and resistance
Fouling depends on: concentration, temperature
pH, molecular interactions

Resistances-in-series model to describe the flux decline:

flux, J
P
J
Rm  Rc  time, t
 Fouling and resistance
The build-up layer and the clogging gel layer porous
of the pores are referred to as a membrane
fouling layer.
Rp : pore  blocking Rp
Ra : adsorption
Rm : membrane Ra
Rg : gel layer formation
Rm
Rcp : concentration polarization

Rm= Rm(t=0)+Ra+Rp;
Rc=Rg+Rcp
Rtot=Rm+Rc
Rcp R g
 Methods to reducefouling
a. Heat treatment
1. Pretreatment of the feed solution
b. pH adjustment
c. Addition of complexing agents
d. Chlorination
e. Adsorption onto active carbon
f. Chemical clarification

2. Membrane properties a. Narrow pore size distribution

b. Hydrophilic membranes

a. Reducing concentration polarisation

a1. Increasing flux velocity
3. Module and process conditions a2. Using low flux membranes
b. Turbulence promoters
a. Hydraulic cleaning
4. Cleaning Back-flushing b. Mechanical cleaning
c. Chemical cleaning
d. Electric cleaning
 Ultrafiltration & Nanofiltration

• Ultrafiltration and nanofiltration is similar

to microfiltration, except the pore size is
even smaller (on the order of the
molecule size) and the number of pores
small.
• This allows for separation of smaller
components, for example separating a
small molecule from solvent.
 Some industrial applications
1. Waste-water treatment
2. Clarification of fruit juice, wine and beer
3. Ultrapure water in the semiconductor industry
4. Metal recovery as colloidal oxides or hydroxides
5. Cold sterilization of beverages and pharmaceuticals
6. Medical applications: transfusion filter set, purification of
surgical water
7. Continuous fermentation
8. Purification of condensed water at nuclear plants
9. Separation of oil-water emulsions
 Pore geometries

J – the solvent flux

P – pressure difference
x – thickness of membrane
Hagen-Poiseuille equation
  tortuosity
  viscosity
ε d 2
ΔP d – the pore diameter
J   – the surface porosity
32  η  τ Δx
 Pore geometries

S – the internal surface area

K – Kozeny-Carman constant

Kozeny-Carman
relationship

ε 3
ΔP
J 
K  η S  1 ε 
2 2
Δx
 Pore geometries

top layer thickness

0.1-1m

sub layer thickness

50-150m

The flux is inversely proportional commercial

to the thickness. interest
 Ultrafiltration
Applications:

•food and dairy industry (the concentration of milk and cheese

making, the recovery of whey proteins, the recovery of potato starch
and proteins, the concentration of egg products, the clarification of
fruit juices and alcoholic beverages)
•pharmaceutical industry (enzymes, antibiotics, pyrogens)
•textile industry
•chemical industry
•metallurgy (oil-water emulsions, electropaint recovery)
•paper industry
•leather industry
•sub layers in composite mebranes for nanofiltration, reverse osmosis,
gas separation or prevaporation
 Ultrafiltration
Factors affecting the performance:

•flow across the membrane surface

high flow velocity high permeate rate

• operating pressure
due to increased fouling and compaction,
pressures rarely exceed 100 psig (1 psig=0.068948 bar)

• operating temperature
high temperature high permeate rate
 Nanofiltration
• Used when low molecular weight solutes as inorganic salts
or small organic molecules (glucose, sucrose) have to be
separated.

• pore size < 2 nm

• the operating pressure 10-20 bar
• material directly influences the separation
• nanofiltration membranes are considered
intermediate between porous and nonporous membranes
• most of the nanofiltration membranes are charged
• two models for the separation mechanism
1.permeation through a micropore
2.the solution-diffusion into the membrane matrix
 Nanofiltration
Applications:

• desalination of brackish and seawater to produce potable

water

• producing ultrapure water for the semiconductor industry

• retention of bivalent ions such as Ca2+, CO 2-

• retention of micropollutants and
microsolutes insecticides, pesticides, dyes, sugar
 Recap:
• Membrane performances depend on the
following parameters:
• Physical
• – porosity, pore size and pore distribution,
thickness, tortuosity, thermal stability etc.
• Chemical
(a) Surface and electrochemical
– streaming potential, zeta potential (electro
kinetic), surface charge density etc.

(b) Electrical
• – impedance measurements to determine
the membrane conductance and
capacitance
Membrane Physical Properties

Some of the more common parameters used

to characterize microporous membranes
include the following:
• Pore diameter – range of pore sizes
• Porosity – fraction of total membrane volume that is
porous. Typical average porosities from 0.3 to 0.7
• Tortuosity - length of the average pore compared to
the membrane thickness. Typical range 1.5 to 2.5
• Thermal stability – at low T, polymers can be
classified as glassy or crystalline.
 Evaluation of Membrane Performance
• Membrane performances are evaluated using the following parameters:
1. Permeation Flux
• Definition: the volume flowing through the membrane per unit area per unit
time. The SI unit used is m3/m2.s
• For the case of transport of gases and vapors, the volume is strongly
dependent on pressure and temperature. As such, gas fluxes are often
given in terms of a "standard condition“ which is defined as 0oC and 1
atmosphere (1.0013 bar).
tortuosity
2. Permeability Coefficient (P)
Definition: the transport flux of material through the membrane
per unit driving force per unit membrane thickness. It's value must
be experimentally determined. The barrer is the commonly used
unit for gas separation and it is defined as:

In general, permeability of a polymer for a gas mixture increases

with decreasing size and increasing solubility (or condensability) of
the gas. The relative permeability of a gas is given below in order of
decreasing gas permeability as:
 Exercises
Look up example:
13.4-1
13.4-2
13.4-3
13.9-1
13.9-2