Membrane Separation Processes

By

Dr. Nadeem Feroze

DEPARTMENT OF CHEMICAL ENGINEERING

Introduction
Effective product separation is very crucial to
economic operation in the process industry.
Some materials are very much difficult to separate
examples are
Dispersed solids ( compressible or density close to
liquid phase)
Low molecular weight, non-volatile organics,
pharmaceuticles, dissolved salts
Biological materials

Introduction
The processing of these categories of materials has
become important
Newer biotechnological industries
Sophisticated nature of processing in food industries

Nature has the answer

Highly effective

Energy efficient though slow in process terms

Nature separates biologically active materials by means
of membranes

 Membranes are defined as an interphase

separating two phases and selectively
controlling the transport of materials between
those phases
A membrane is an interphase rather than
interface because it occupies it a finite,
though normally small, element of space.

 Human beings are surrounded by membranes

Skin
Kidney
Liver
Membranes control the separation of
materials at all levels of life, down to the outer
layers of bacteria and subcellular components.

 Synthetic membranes have been developed

for conventially difficult separations.
It offers advantage of ambient temperature
operation, relatively low capital and running
costs, modular construction.

Classification of Membrane Processes

Industrial membrane processes may be classified according to the
size range of materials which they are to separate and the driving
force used in separation.

Discussion will be concerned with pressure driven processes

Microfiltration
Ultrafiltration
Nanofiltration
Reverse Osmosis

These are already well established large scale industrial processes.

RO is a widely used separation process.

Classification of Membrane Separation Processes for

Liquid Systems

Nature of Synthetic Membranes

Membranes used for pressure driven separation
processes are most commonly made of polymeric
materials.
Initially most membranes were cellulosic in nature
but are now replaced by advance polymers such as
polyamide, polysulphone, polycarbonate.

These synthetic polymers have better resistance to

microbial degradation and improved Chemical
stability

Membrane development process

a) Polymer is dissolved in a solvent 10-30 percent
by mass
b) Resulting solution is cast on a suitable support
as a film of thickness 100 micrometer
c) Film is quenched by immersion in a non-solvent
bath, typically water or non aqueous solution
d) Resulting membrane is annealed by heating
This process is known as immersion precipitation

Contd.
The ultimate membrane structure results as a
combination of phase separation and mass
transfer, variation of the production
conditions giving membranes with different
separation characteristics.
Most microfiltration membranes have a
symmetric pore structure, and they can have a
porosity as high as 80 per cent.

 Ultrafiltration and reverse osmosis membranes have an

asymmetric structure comprising a 12 m thick top layer of
finest pore size supported by a 100 m thick more openly
porous matrix, as shown in Figure.
Such an asymmetric structure is essential if reasonable
membrane permeation rates are to be obtained

 Another important type of polymeric membrane is

the Thin-film Composite membrane.

This consists of an extremely thin layer, typically

1 m, of finest pore structure deposited on a
more openly porous matrix. The thin layer is
formed by phase inversion or interfacial
polymerization on to an existing microporous
structure.

Inorganic Membranes
Recent advancement has been the development of
Microfiltration and Ultrafiltration membranes
composed of inorganic oxide materials presently
produced by two main techniques
1. Depositon of collodial metal oxide on to a
supporting material such as carbon
2. Puerly ceramic materials by high temperature
sintering of spray dried oxide microspheres.

Advantages of inorganic membranes

Higher temperature stability
Steam sterilisation
Increased resistance o fouling
Narrow pore size distribution

 A parameter often quoted in manufacturers literature is

the nominal molecular weight cut-off (MWCO) of a
membrane.
This is based on studies of how solute molecules are
rejected by membranes.
A solute will pass through a membrane if it is sufficiently
small to pass through a pore, if it does not significantly
interact with the membrane and if it does not interact
with other, larger solutes

 It is possible to define a solute rejection

coefficient R by:
R = 1 - (Cp/Cf)
Cf = concentration of solute in the feed stream
Cp = concentration of solute in permeate

 For a given ultrafiltration

membrane with a
distribution of pore sizes
there is a relationship
between R and the solute
molecular weight, as
shown in Figure
The nominal molecular
weight cut-off is normally
defined as the molecular
weight of a solute for
which R = 0.95.

General Membrane Equation

The general membrane equation is an attempt to state the
factors which may be important in determining the
membrane permeation rate for pressure driven processes

Where
J is the membrane flux, expressed as volumetric rate per unit area
|P| is the pressure difference applied across the membrane.
is the difference in osmotic pressure across the membrane
Rm is the resistance of the membrane
Rc is the resistance of layers deposited on the membrane, the filter cake and gel foulants.

Membrane Modules
In industry the equipment for MF, UF, and RO is
applied in form of modules
Membrane area is in the range of 1-20 m2
Modules can be connected in parallel or in series
Commonly used modules are

Tubular
Flat sheet
Spiral wound
Hollow fibre

Tubular modules
Used in turbulent flow regime
Concentration of high solids content feed
Membrane is cast on the inside of a porous support which
is often housed in a perforated stainless steel pipe
Individual modules contain a cluster of tubes in series held
with in a stainless steel permeate
Diameter in 10-25 mm , 1-6 m length
Feed is pumped through the tubes with Reynold Number
greater than 10,000
Can be easily cleaned
Main disadvantages are the relatively low membrane
surface area and higher volumeric hold up

Flat sheet modules

Similar to conventional filter
presses
Consists of annular membrane
discs of outer diameter 0.3 m
Suitable for laminar flow
A single module contains 19 m2
of membrane area
Permeate is collected from each
membrane so that damaged
membranes can be easily
identified
Replacement of membrane
requires dismantling of the
whole stack

Spiral-wound modules

Consist of several flat membranes

separated by turbulence-promoting
mesh separators and formed into a
Swiss roll

This produces a cylindrical module

which can be installed within a
pressure tube.

Feed enters at one end of the

pressure tube and encounters a
number of narrow, parallel feed
channels formed between adjacent
sheets of membrane.

Permeate spirals towards the

perforated central tube for
collection.

Up to six such modules may be

installed in series in a single pressure
tube.

Hollow-fibre modules
Consist of bundles of fine
fibres, 0.12.0 mm in
diameter, sealed in a tube.
For desalination
applications, feed flow is
usually around the outside
of the unsupported fibres
with permeation radially
inward.
Capable of high pressure
operation
Readily fouled and difficult
to clean

Plant Configuration
Membrane modules can be configured in various
ways to produce a plant of the required separation
capability.

A simple batch recirculation system arrangement is

most suitable for small-scale batch operation.
Larger scale plants will operate either as feed and
bleed or continuous single-pass operations

Feed and bleed

Retentate is initially totally recycled
When the required solute concentration is reached within the loop, a fraction of
the loop is continuously bled off.
The main advantage is that the final concentration is then continuously available as
feed is pumped into the loop.
The main disadvantage is that flux is lower than the average flux in the batch mode,
with a correspondingly higher membrane area requirement.

Feed and bleed

Large-scale plants usually use multiple stages operated in series to overcome the
low-flux disadvantage of the feed and bleed operation.
Only the final stage is operating at the highest concentration and lowest flux,
while the other stages are operating at lower concentrations with higher flux.
Thus, the total membrane area is less than that required for a single-stage
operation.

Continuous single pass

Concentration of the feed stream increases gradually along the length of
several stages of membrane modules arranged in series.
The feed only reaches its final concentration at the last stage.
There is no recycle and the system has a low residence time.

Reverse Osmosis

Introduction
When miscible solutions of different concentration are
separated by a membrane that is permeable to the
solvent but nearly impermeable to the solute, diffusion
of the solvent occurs from less concentrated to the more
concentrated solution, where solvent activity is lower.
The diffusion of solvent is called Osmosis.

Osmotic transfer of water occurs in many plant and

animal cells

Introduction
The transfer of solvent can be stopped by increasing the
pressure of the concentrated solution until the activity of
solvent is same on both sides of the membrane.
If pure solvent is on one side of the membrane, the
pressure required to equalize solvent activities is the
osmotic pressure of the solution.

If pressure higher than the osmotic pressure is applied,

solvent will diffuse from concentrated solution to dilute
solution. This Phenomenon is called Reverse Osmosis

Osmosis and Reverse Osmosis Illustration

Basic Terminology
Feed water: Supply water that is fed into the RO system to be
treated
Permeate: A portion of the feed water that passes through a series
of membranes and is returned as purified water.
Concentrate: A portion of the feed water that is rejected by the
membrane and contains the solution of impurities that have been
filtered out of the permeate.
Water flux: The rate of permeate production typically expressed as
the rate of water flow per unit area of membrane (e.g., gallons per
square foot per day)
Recovery rate: The ratio of permeate flow to feed water flow, which
indicates the overall water efficiency of the system

Basic Information

RO Membrane Properties
More than 50% of RO modules use cellulose acetate
membrane.
It has high permeability for water and low permeability for
dissolved salts.
Its limitation are:
I.
II.

III.

Smaller allowable pH range of 4.5-7.5 (beyond this range, cellulose

acetate becomes prone to hydrolysis)
Susceptibility to biological attack (degradation due to growth of
microbes)
Reduction of solvent flux because of compaction or mechanical
compression of membrane at high pressure difference

RO Membrane Properties
Another common membrane materials in RO systems
are thin film composite (TFC) membranes.

TFC membranes are not chlorine-tolerant but can

tolerate harsh chemical environments and wide ranges in
water temperature and pH, and are less vulnerable to
compaction than CA membranes.
TFC membranes generally have higher water flux than CA
membranes because the layers are extremely thin, which
creates more water transport through the membrane
material.

Membrane Configuration
Spiral Wound
Plate and Frame
Hollow fibre
Tubular

Applications
Potable water from sea or brackish water
Ultra pure water for food processing and
electronic industries
Pharmaceutical grade water
Water for chemical, pulp & paper industry
Wastewater treatment
Municipal and industrial waste treatment

Mechanism
The mechanism of water and salt transport in
reverse osmosis is not completely understood.
One theory is that water and solutes diffuse
separately through the polymer by a solutiondiffusion mechanism.

In this mechanism concentration of water in dense

polymer is assumed to be proportional to the activity
of water in the solution

Mechanism
On the low-pressure side of the dense layer, activity is
essentially unity if nearly pure water is produced at 1 atm.
On the high-pressure side, activity would be

slightly less than 1.0 at atmospheric pressure

1.0 at atmospheric pressure
slightly greater than 1.0 at higher pressures

The upstream pressure is generally set at 20 to 50 atm above

the osmotic pressure of the feed solution.
At these pressures, activity of water aW is only a few percent
greater than for pure water at 1 atm and change in activity
and concentration across the membrane are small

 The Driving force for water transport is the difference

in activity, which is proportional to pressure
difference in osmotic pressures of feed and product.
The equation for water flux is

Dw is the diffusivity in the membrane

Cw is the average water concentration (g/cm3)
Vw is the partial molar volume of water (cm3/gmol)

 The flux of solute is assumed proportional to the

difference in solution concentration, the diffusivity
and a solubility or distribution coefficient.

Concentration Polarization
Nearly complete rejection of solute by the membrane
leads to a higher concentration at the membrane surface
than in bulk solution and this effect is called
Concentration polarization.
Concentration polarization reduces the flux of water
because the increase in osmotic pressure reduces the
driving force for water transport.
The solute rejection decreases both because of the lower
water flux and the greater salt concentration at the
surface increases the flux of solute

Concentration Polarization
Equations for concentration polarization have been derived for simple
cases such as laminar flow of feed solution inside hollow fibres.
Consider a membrane with a water flux Jw when the bulk solute
concentration is cs and f is the fraction of solute rejected.
Diffusion of solute away from membrane surface is characterized by mass
transfer Coefficient kc and driving force csi cs .
At steady state, diffusional flux equals the amount of solute rejected per
unit area

Jw cs f = kc (csi cs)
Polarization factor is defined as

Jw f (csi cs)
=
kc
cs

Factors that impact on RO performance

Basic effects of:

Temperature
Pressure
Recovery rate

Temperature Effects
RO permeate flow is strongly dependent on the
temperature of the feed water.
The higher the temperature the higher the permeate
flow rate.
Why? Lower viscosity makes it easier for the water to
permeate through the membrane barrier
RULE OF THUMB for every 1C the permeate flow
will increase ~ 3%

Temperature Variation on Salt flux

Solute rejection declines with a temperature rise because
of the osmotic pressure increase with temperature.
Increasing temperature increases salt passage more than
water passage
Generally you will get better rejections at lower
temperatures
RULE OF THUMB salt flux increases 6% for 1C increase

Pressure Effects
Water passage increases with pressure. Solute
rejection rises with pressure, since solvent flux
increases and solute diffusion does not.
Higher flow of water through the membrane will tend
to promote more rapid fouling, the single greatest
cause of membrane failure.
Membrane element manufacturers usually provide
limits with regard to the maximum applied pressure to
be used, as a function of feed water quality.

Recovery rate Effects

As recovery is increased, concentration of solute in the
concentrate stream increases, resulting in increased
osmotic pressure which must be overcome.
Membrane flux declines with increasing solute
concentration at high recovery rate.
Large systems typically have recovery rates between
40% and 60%. In other words, for every 10 gallons of
feed water entering the system, 4 to 6 gallons of
purified permeate water are produced

Steps to design RO membrane system

1. System Design Information and Feed Water
2. Selection of Element Type and Average Permeate
Flux
3. Calculation of Number of Total RO Elements
4. Decision of Recovery Rate
5. Decision of Number of Stages
6. Decision of Number of RO Elements per Pressure
Vessel
7. Decision of Element Arrangement

1. System Design Information and Feed Water

The RO membrane system highly depends on the available
feed water.
Therefore, the system design information (required product

flow rate, expected recovery rate, annual water temperature,

water source, application, pretreatment, required product water
quality, operating pressure limit, etc.) and the feed water

analysis should be thoroughly studied and considered in

selection of the RO system design.
If the required permeate water quality is so high that the
quality cannot be achieved by 1pass RO system, and then a
2 pass RO system should be considered

2.

Selection of Element Type and Average

Permeate Flux

According to the feed water source, pretreatment and feed water

salinity, the type of RO membrane element is selected.
Consider the following characteristics while selecting particular
membrane for an application:

Membrane fouling rates

Water flux specification
Solid rejection rate
System pressure requirements
Membrane response to cleaning operations and tolerance of
cleaning procedures
Tolerance of pH
Temperature range
Chemical abrasion resistance

Contd
Once the water source, pretreatment and RO
element type are fixed by the designer, the
recommended value of the average permeate flux
(also called design flux) is given.
In some cases, the design flux value is determined by
pilot experiment data or customers experience.

3.

Calculation of Number of Total RO Elements

The relationship between the number of total elements, the product

flow rate and the average permeate flux is expressed as follow equation:

In which:
NE = total element numbers
Qp = product flow rate
JV, ave = average permeate flux
(MA)E = membrane area of element

The calculated number of RO elements may be a slightly changed based on the

decision of element arrangement, that is, the number of pressure vessel and RO
elements per pressure vessel.

4.

Decision of Recovery Rate

In an RO membrane system, a recovery rate as high as

possible is desirable, but a high recovery rate can also cause
some problems as follows
Possibility of scale formation increase because of the increase
of concentration factor
Osmotic pressure increase because of the increase of
concentration factor
Concentrate flow rate decrease
Permeate water quality deterioration because of average feed
concentration increase

Contd
The relationship between recovery rate and concentration
factor is shown in Table

Usually in brackish water desalination, the recovery rate is

decided by scale formation, and in seawater desalination, by
feed pressure limit.

5.

Decision of Number of Stages

The number of RO stages defines how

many pressure vessels are in series in
the RO membrane system.
Every stage consists of a certain
number of pressure vessels in parallel
The number of stages is a function of
the system recovery rate, the number
of elements per vessel, and the feed
water quality as shown

6.

Decision of Number of RO Elements per

Pressure Vessel

RO membrane elements can be coupled together in series

in the pressure vessel, typically 1-8 elements per one
pressure vessel.
In deciding the number of RO elements per pressure vessel,
plant size is usually considered first.
In a large-scale plant (> 40 m3/h), 6-8 elements per
pressure vessel are usually adopted, and in a smaller plant,
3- 5 elements per pressure vessel.
In all cases, the space required to install or remove the RO
elements should be considered in the plant design.

Contd
By increasing the number of RO elements per pressure vessel,
almost all RO design parameters will change.
Table shows RO system design parameters and the correlation
between an increase in number of RO element per pressure vessel,
and change in RO system design parameters.

7.

Decision of Element Arrangement

The RO element arrangement (array) means element

numbers per vessel, vessel numbers per stage and stage
numbers per pass.
For the decision of element arrangement, the system
design parameters should be consistent with the design
flux guideline.
In the case that not every parameter is in accordance with
the design guideline, it is necessary to make a priority in
the parameters. Usually average permeate flux,
concentrate flow rate and pressure drop per vessel should
be of higher priority.

Contd
To decide the array, several calculations for case study
should be done by computer program and these results
should be compared.
Some case studies should be done with the consideration
of different operating conditions (feed concentration,
temperature, etc.) or performance changes with time.
For each typical case, a comparison should be done in
consideration of value of design parameter, the numbers of
RO elements or pressure vessel, and satisfying the
customers demand (product water quality, limit of feed
pressure etc.).

RO System Components
RO systems consist of the following basic components, which are
common to every RO system. The specifications for each
component vary by application, source water quality, and the
required permeate quality.

Pre-filter(s): It is common for pre-filters to pretreat the feed

water supply before it enters an RO system. Multiple prefilters may be used in an RO system. The most commonly used
pre-filters are sediment filters used to remove sand, silt, dirt,
and other sediment. Carbon filters also may be used to
remove chlorine and organic compounds

RO System Components
Reverse osmosis membrane: The RO membrane is the heart of the
system. The membrane is where the contaminants are trapped in
the concentrate and purified water is produced.
Pressure vessels: A pressure vessel is a sealed hollow tube that
houses the RO membrane elements. To force water through a semipermeable membrane, pressure must be applied to overcome the
feed waters osmotic back pressure and permeate back pressure
Pumps: Pumps are required to push the water through the RO
system. They must be sized to meet the required operating
pressure and flow rate of the system and they constitute largest
energy consuming component in the system

RO System Components
Valves: Valves are required to control the flows and pressures
of an RO system for the system to operate correctly and
optimally. There are generally two valves in an RO unit on the
feed water piping and on the concentrate piping.
Storage tank: Permeate is stored in tanks. Industrial and
commercial storage tanks may hold up to 9000 gallons of
water.
Drain line: This line runs from the outlet end of the RO
membrane housing to the drain. This line is used to dispose of
the concentrate rejected by the membrane element

Diagram of an RO System with Basic

Components

REVERSE OSMOSIS WATER TREATMENT PLANT

The largest scale applications of membrane separation processes
are those which form the key step in the desalination, or more
generally demineralization, of brackish water in the production of
drinking water.
An outline is given of such a plant capable of producing 70,000
m3/day of drinking water for a large city in the Middle East
The water to be processed is obtained from a deep well with a total
dissolved solids (TDS) content of 1.4 kg/m3; that is, it is of moderate
salinity and hardness.
The plant specification required that the product water should have
a maximum TDS of 0.5 kg/m3

Flow diagram of reverse osmosis plant for

demineralization of Brackish water

Main Process Steps

Pretreatment
a.

Evaporative cooling to reduce the feed water temperature from

5055C to 3035C which is more compatible with satisfactory
operation of the reverse osmosis unit and more suitable for final
use.

b.

Precipitation softening by addition of slaked lime (Ca(OH)2) and

sodium aluminate or ferric chloride. The net result is part-removal
of calcium, silica and especially colloids. The clarifiers used ensure
completion of these processes within the tank.

c.

Acidification to optimise removal of residual coagulant.

d.

Prechlorination to ensure a disinfected supply to the reverse

osmosis plant

Pretreatment
e.

Rapid gravity filtration to reduce further the content of particulate

material.

f.

Acidification to reduce the pH to 5.0 for optimum life of the

reverse osmosis membrane.

g.

Sequestering, addition of sodium hexametaphosphate to retard

the precipitation of calcium sulphate which otherwise will exceed
its solubility limit in the reject stream.

h.

Cartridge filtration with elements rated at 25 m to protect the

high pressure pumps and reverse osmosis membranes in the
event of a break-through of particulate material.

Demineralization by reverse osmosis

Reverse osmosis was chosen for the demineralization step as
it gave an economic solution in terms of both capital and
running costs.
It allowed a high water recovery rate, was modular in
construction and so could be easily extended, could cope with
reasonable variations in feed salinity.
The pre-booster pumps, cartridge filters and high pressure
pumps are arranged in seven parallel streams, one of which is
on standby
A total of thirteen reverse osmosis stacks is installed, any
twelve of which will meet the required throughput

Demineralization by reverse osmosis

Each stack contains 210 reverse osmosis modules
accommodated in 35 pressure vessels arranged in a
seriesparallel array of 20105 to achieve the desired
water recovery
These modules are of the spirally wound type.
The permeate from the unit is blended with the
slipstream flow, with pH adjustment if necessary, to
maintain a final water TDS < 0.5 kg/m3.
The reject is discharged to evaporation ponds.

Separation of Gases

Porous Membranes
When a gas mixture is allowed to diffuse through a
porous membrane to a region of lower pressure, gas
permeating the membrane is enriched in low molecularweight components since they diffuse more rapidly.
When the pores are much smaller than mean free path in
the has phase, the gases diffuse independently by
Knudsen Diffusion.
Diffusivity in the pore is proportional to the pore size and
average molecular velocity, which varies inversely with
the square root of molecular weight.

Contd
The flux per unit membrane area depends on an
effective diffusivity De that is lower than the pore
diffusivity by the factor (/) where is the porosity
and the tortuosity.
For membranes with about 50% porosity, this factor
is generally 0.2 to 0.3

 The flux of each gas is proportional to the concentration

gradient, which is linear if the membrane structure is
uniform and the gases do not interact.
Usually the gradient is expressed as a partial pressure
gradient and ideal gases are assumed

The composition of the permeate depends on the fluxes

of all species. For a binary system, mole fraction of A in
the permeate is

Typical Pressure gradients in a porous membrane

Polymer Membranes
The transport of gases through dense (non-porous) polymer
membranes occurs by a solution-diffusion mechanism.
The gas dissolve in the polymer at the higher pressure side of
membranes, diffuses through the polymer phase, and desorbs
or evaporates at the low pressure side.
The rate of the mass transfer depends on the concentration
gradient in the membrane, which is proportional to the partial
pressure gradient if solubility is proportional to the pressure.

Gradients in a dense Polymer Membrane

Henrys law is assumed to

apply for each gas and
equilibrium is assumed at
the interface.
The gas-film resistances
are neglected for this
case, so the partial
pressures at the gaspolymer interface are
same as those in the bulk

 The flux for gas A is

The concentrations are related to the partial pressures by a

solubility coefficient S, which has units such as (mol /cm3.atm)

Replace the concentration gradient with a pressure gradient

gives

The product DASA is the flux per unit pressure gradient, which is called
permeability coefficient qA and often expressed in Barrers.

 Since the actual membrane thickness is not always known or

specified for commercial membranes, it is customary to use
the flux per unit pressure difference, which will be called the
permeability (QA)

The ratio of permeabilities for a binary mixture is the

membrane selectivity (also called the ideal separation
factor)

A high selectivity can be obtained from either a favorable diffusivity ratio

or large difference in solubilities.
The diffusivities in the membrane depend more strongly on the size and
shape of molecules than do gas phase diffusivities

 Permeabilities reported for light gases in a few polymers are

listed in table

The permeabilities are much greater for rubber and silicone

than for polysulfone and other glassy polymers.
The permeability goes through a minimum with increasing
molecular weight or size of the gas molecule.

Pervaporation

Introduction
Pervaporation is a separation process in which one or
more components of a liquid mixture diffuse through
a selective membrane, evaporate under low pressure
on downstream side and are removed by a vacuum
pump or a chilled condenser.
The process differs from other membrane processes
in that there is a phase change from liquid to vapor
in the permeate.

Introduction
The driving force in the membrane is achieved by
lowering the activity of the permeating components at
the permeate side.
Components in the mixture permeate through the
membrane and evaporate as a result of the partial
pressure on the permeate side being held lower than the
saturation vapor pressures.

The driving force is controlled by applying a vacuum on

the permeate side

Schematic Diagram of Pervaporation unit

 Composite membranes are used with dense layer in

contact with the liquid and the porous supporting layer
exposed to the vapor.
Pervaporation is favored when the feed solution is dilute
in the main permeant because sensible heat of the feed
mixture provides the permeant enthalpy of vaporization
The phase change occurs in the membrane and the heat
of vaporization is supplied by the sensible heat of the
liquid conducted through the thin dense layer.

 The decrease in temperature of the liquid as it

passes through the separator lowers the rate of
permeation and this usually limits the application
of pervaporation to removal of small amounts of
feed.
Commercial units generally use flat-sheet
membranes stacked in filter press arrangement.
Spiral-wound membranes could also be used.

Applications
Dehydration of ethanol or the production of high purity
ethanol by a hybrid process which also incorporates
distillation.
Such separations use cellulose-acetate-based compositemembranes, with an active layer of polyvinyl alcohol.
Membranes used for ethanol purification are also suitable for
dehydration of many other organic solvents including
methanol, isopropanol, butanol, MEK, acetone and
chlorinated solvents.

Applications
Removal of volatile organic contaminants from water
using silicone rubber or organophilic polymers for the
membrane.
The separation of close-boiling organic mixtures like
benzenecyclohexane is receiving much attention.
Separating benzene from cyclohexane consisting of a
cellulose acetate support matrix and incorporating
polyphosphonates to improve the preferential
permeability of benzene.

Comparison of ethanolwater separabilities

Pervaporation Processes

Hybrid process for removal of water from ethanol

Dehydration of dichloroethylene.

Removal of volatile organic compounds (VOCs) from

wastewater

Membrane Selection and Modules

Membrane selection is critical in the commercial
application of PV.
For water permeation, Hydrophilic membrane materials
are preferred.
For example, a three-layer composite membrane is used for
the dehydration of ethanol, with water being the main
permeating species.

The support layer is porous polyester, which is cast on a

microporous polyacrylonitrile or polysulfone membrane.
The final layer, which provides the separation, is dense PVA
of 0.1 mm in thickness.

 Hydrophobic membranes, such as silicone rubber and Teflon,

are preferred when organics are the permeating species.
Commercial membrane modules for PV are almost exclusively
of the Plate-and-frame type because of the ease of using
gasketing materials that are resistant to organic solvents and
the ease of providing heat exchange for vaporization and
high-temperature operation.
Hollow-fiber modules are used for removal of VOCs from
wastewater. Because feeds are generally clean and operation
is at low pressure, membrane fouling and damage is minimal,
resulting in a useful membrane life of 24 years.

Mechanism
The flux of each component is proportional to the concentration
gradient and the diffusivity in the dense layer.
However, the concentration gradient is often non-linear because
the membrane swells appreciably as it absorbs liquid.
Diffusion coefficient in the fully swollen polymer may be 10 to 100
times the value in unswollen polymer.
When the polymer is swollen mainly by absorption of one
component, the diffusivity of other components is increased also.
This interaction makes it difficult to develop correlations for
membrane permeability and selectivity.

Mechanism
Models for transport of permeant through a membrane by
pervaporation have been proposed, based on solutiondiffusion.
They assume equilibrium between the upstream liquid and
the upstream membrane surface & between the
downstream vapor and its membrane side.
Membrane transport follows Ficks law, with a permeant
concentration gradient as the driving force.
However, because of phase change and non ideal-solution
feed, simple equations do not apply.

Mechanism
A convenient PV model is that of Wijmans and Baker
who express the driving force for permeation in terms of
a partial-vapor-pressure difference.
Pressures on both sides of the membrane are low, the
gas phase follows the ideal-gas law.
Therefore, at the upstream membrane surface (1),
permeant activity for component i is

where Psi is the vapor pressure at the feed temperature

Mechanism
Liquid on the upstream side of the membrane is generally
non-ideal. Thus
Combining both equations

On the vapor side of the membrane (2), partial pressure is

Thus, the driving force can be expressed as

Mechanism
If non-linear effects are neglected than the corresponding
permeant flux, after dropping unnecessary superscripts, is

where
PMi is called permeability coefficient expressed in Barrers units
is termed as Permeability

In commercial applications of PV, liquid feed usually has a low concentration of

the more permeable species, so swelling of the membrane and resulting nonlinear effects are not as pronounced as when testing solutions of high
concentration.

Gradients in a Pervaporation membrane

DIALYSIS

Introduction
In a dialysis membrane-separation process, the feed is a liquid,
at pressure P1, containing solvent, solutes of type A, and solutes
of type B and/or insoluble, but dispersed, colloidal matter.
A sweep liquid or wash of the same solvent is fed at pressure P2
to the other side of the membrane.
The membrane is thin with micropores of a size such that solutes
of type A can pass through by a concentration driving force.
Solutes of type B are larger in molecular size than those of type
A and pass through the membrane only with difficulty or not at
all.

Introduction
Colloids do not pass through the membrane.
With pressure P1 = P2, the solvent may also pass through
the membrane, but by a concentration-driving force
acting in the opposite direction.
The transport of the solvent is called osmosis.

By elevating P1 above P2, solvent osmosis can be

reduced or eliminated if the difference is higher than the
osmotic pressure.

Contd
The products of a dialysis unit (dialyzer) are a liquid
diffusate (permeate) containing solvent, solutes of
type A, and little or none of type B solutes; and a
dialysate (retentate) of solvent, type B solutes,
remaining type A solutes, and colloidal matter.
Ideally, the dialysis unit would enable a perfect
separation between solutes of type A and solutes of
type B and any colloidal matter

Example
When dialysis is used to recover sulfuric acid (type A
solute) from an aqueous stream containing sulfate salts
(type B solutes), the following results are obtained

Thus, about 64% of the H2SO4 is recovered in the

diffusate, accompanied by only 6% of the CuSO4, and no
NiSO4.

Applications
Recovery of chromic, hydrochloric, and hydrofluoric acids from
contaminating metal ions.
Removal of alcohol from beer to produce a low-alcohol beer.
Recovery of nitric and hydrofluoric acids from spent stainless steel pickle
liquor.
Removal of mineral acids from organic compounds.
Removal of low-molecular-weight contaminants from polymers.
Hemodialysis, in which urea, creatine, uric acid, phosphates, and chlorides
are removed from blood without removing essential higher-molecular
weight compounds and blood cells in a device called an artificial kidney

Membrane Types & Modules

Typical microporous-membrane materials used in dialysis are
hydrophilic, including cellulose, cellulose acetate, various acidresistant
polyvinyl
copolymers,
polysulfones,
and
polymethylmethacrylate.
Typically less than 50 mm thick and with pore diameters of 15
to 100
The most common membrane modules are plate-and-frame
and hollow-fiber.
Dialysis membranes can be thin because pressures on either
side of the membrane are essentially equal.

Contd
A common dialyzer is the plate-and-frame type. For
dialysis, the frames are vertical and a unit might
contain 100 square frames, each 0.75 m 0.75 m on
0.6-cm spacing, equivalent to 56 m2 of membrane
surface.
Recent dialysis units utilize hollow fibers of 200-mm
inside diameter, 16-mm wall thickness, and 28-cm
length, packed into a heat exchanger- like module to
give 22.5 m2 of membrane area.

Contd
In a plate-and-frame dialyzer, the flow pattern is nearly
countercurrent.
Because total flow rates change little and solute
concentrations are small, it is common to estimate solute
transport rate by assuming a constant overall masstransfer coefficient with a log-mean concentrationdriving force

Rate Equation
The differential rate of solute mass transfer across
the membrane is

where Ki is the overall mass-transfer coefficient, in terms of

the three coefficients

where kiF and kiP are mass-transfer coefficients for the feedside and permeate-side boundary layers (or films)

Contd
If a solute does not interact with the membrane material,
effective diffusivity De , is the ordinary molecular-diffusion
coefficient, which depends only on solute and solvent
properties.
In practice, the membrane may have a profound effect on
solute diffusivity if membranesolute interactions such as
covalent, ionic, and hydrogen bonding; physical adsorption
and chemisorption; and increases in membrane polymer
flexibility occur.
Thus, it is best to measure PMi experimentally using process
fluids.

 Transport of solvents such as water, usually in a direction

opposite to the solute, can be described in terms of Ficks law
It is common to measure the solvent flux and report a socalled water-transport number, which is the ratio of the
water flux to the solute flux, with a negative value indicating
transport of solvent in the solute direction
Design parameters for dialyzers are best measured in the
laboratory using a batch cell with a variable-speed stirring
mechanism on both sides of the membrane so that external
mass-transfer resistances, 1/kiF and 1/kiP are made negligible

 A common dialyzer is the plate-and-frame type.

For dialysis, the frames are vertical and a unit
might contain 100 square frames, each 0.75 m
0.75 m on 0.6-cm spacing, equivalent to 56 m2 of
membrane surface.
Recent dialysis units utilize hollow fibers of 200mm inside diameter, 16-mm wall thickness, and
28-cm length, packed into a heat exchanger- like
module to give 22.5 m2 of membrane area.