National University of Sciences and Technology

(NUST)

Membrane Technology
CHE-442

Instructor: Engr. Arsalan Khalid

Chapter # 1: Introduction
February, 2017

Institute of Environmental Sciences and Engineering (IESE)

School of Civil and Environmental Engineering (SCEE)
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Contents
Membrane Definition
Historical Development of Membranes
Separation Processes
Membrane Separation
Membrane Working Principle
Membrane Performance Parameters
Membrane Classification
Established Membrane Separation Processes
Membrane Advantages and Disadvantages
Membrane Applications
Comprehensive Videos
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What is a Membrane?
A membrane is a selective barrier that allows specific entities to pass
through, while retaining the passage of others when a driving force is
applied across the membranes. Physically membrane could be solid
or liquid.
In membrane separation, a feed consisting of a mixture of two or
more components is partially separated by means of semi permeable
barrier (the membrane) through which one or more species move
faster than another or other species.

Permeable
membrane
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Historical Development of Membranes

In 1748 Abbe Jean-Antoine Nollet; French physicist separated
degassed alcohol using pigs bladder.
1824, Rene- Joachim-Henri Dutrochet, French physiologist introduced
Osmosis: Movement of water through a biological membrane.
1846 Discovery of nitrocellulose (gave scope to MF)
1855 Frick discovered Cellulose nitrate membranes.
1861 Thomas Graham (Father of Modern Dialysis): Coined Dialysis
-Separated Dissolved substances based on mol. wt. & concentration.
1865 Moritz Traube invented first artificial membrane using copper
ferrocyanide precipitates.
1875 Wilhelm Friedrich Philipp Pferrer: Made the membranes to
withstand operational pressures.
1906 Bechhold devised a technique to prepare nitrocellulose
membranes of graded pore size.

R. W. Baker, Membrane Technology and Application, Wiley (Chapter # 1)

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Historical Development of Membranes

1930s Micro porous colloidal membranes became commercially
available.
1950s Development and Significant use of MF technology in the
filtration of drinking water samples at the end of World War II:
Research effort was sponsored by US army.
1959 Samuel Yuster made a breakthrough in RO by the invention
of Loeb-Sourirajan membrane at UCLA.
By 1960 Elements of modern membrane science had been
developed such as Gas Separation, Membrane Distillation etc.
In the early 80s Henis & Tripodi made industrial GS: economically
feasible.
Kober and coworkers developed Pervaporation. Later in 2000s
modified for large scale applications.

R. W. Baker, Membrane Technology and Application, Wiley (Chapter # 1)

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Objective of Separation
Concentration: The desired component is present in a
low concentration and solvent has to be removed

Purification: Undesirable impurities have to be removed

Fractionation: A mixture must be separated into two or

more desired components
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Separation Processes based on Molecular

Properties
Physical /Chemical Separation Processes
Properties
Size MF, UF, Dialysis, Gas separation
Affinity Adsorption/ Absorption RO,
Pervaporation, Gas separation
Charge Ion Exchange, Electro dialysis
Density Centrifugation
Vapor Pressure Pervaporation
Freezing Point Crystallization
Chemical Nature Complexation, Carrier mediated
transport
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Membrane Separation

Permeate Feed

MEMBRANE
Driving Force

Phase 2 Phase 1

Driving Force
C,P,T,E
The term filter is usually limited to structures that separate particulate
suspensions larger than 1 to 10 m.
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Membrane Separation
In membrane separation processes:
the influent to the membrane module is known as the feed stream
(also known as the feed water),
the liquid that passes through the semipermeable membrane is
known as permeate (also known as the product stream or
permeating stream) and
the liquid containing the retained constituents is known as the
concentrate stream also known as retained phase/retentate.
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Natural Membranes
 Membrane Working Principle
Osmosis: when more concentrated solution is separated by semi permeable
membrane flow of less concentrated solution towards the more concentrated
solution takes place due to difference in osmotic pressure of two solution.
Osmotic Pressure
 Osmotic Pressure
Osmotic Pressure in Dilute Solutions:
= iMRT
:M is the molar concentration of the solution.
:R the universal gas constant.
:T the absolute temperature.
: i the dimensionless correction factor.

Osmometric Analysis: To measure osmotic pressure

 Membrane Performance Parameters
Flux:
The flow rate Q through a membrane separation process may be
represented by
Q = kA(P )
k is a membrane permeability coefficient.
A is the membrane superficial area.
P is the pressure drop.
the difference in osmotic pressure between the feed and the permeate.

Membrane flux depends on: Types of Flux:

Membrane volume flux
P mass flux (multiply vol. flux by density)
Osmotic pressure mole flux (divide mass flux by molecular
Cross flow velocity weight)
Temperature
 Membrane Performance Parameters
Transmembrane Pressure (TMP):
It is the pressure gradient that exits through the membrane,
from feed size to permeate size, at each point along the
membrane surface.
 Membrane Performance Parameters
Solute Rejection Coefficient (R): (for aqueous mixtures)
Solute is retained while the solvent molecules pass freely
through the membrane

Cf is the concentration of solute in the feed stream.

Cp is the concentration of solute in the permeate.

Separation Factor: (for gas and organic liquids mixtures)

y concentrations in permeate
x concentrations in feed
chosen such that >1
A/B: A permeates preferentially; B/A: B
A/B =B/A=1 : no separation achieved
 Membrane Performance Parameters
Recovery Percentage:
The relation of the permeate flow rate to the feed flow rate.

%Recovery =

Recovery percentages is inversely proportional with the feed

concentration.

Selectivity:
Ability of a membrane to differentiate amongst entities is
termed its selectivity.
 Membrane Performance Parameters
Molecular Weight Cut-off:
It is the lowest molecular weight solute (in daltons) in which
90% of the solute is retained by the membrane.
Lower molecular weight cut-off (M W C O) => more retention
=> Higher P
 Membrane Performance Parameters
QR, CR
QF, CF

1. Retention Qp Cp

Retention ( R ) = CF-CP = 1 - CP
CF CF
2. Permeate Flux
J = QP / Membrane Area
3. Water Recovery
WF = Q P / Q F
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What is a good Membrane like?

Material Related:
Mechanical durability- easy to handle, wearproof,
pressure resistance
Chemical resistance- to cleaning chemicals, oxidizing
chemicals, acids, alkalines and solvents in chemical
industry
Temperature resistance
Resistant to bacteria, etc. (No Fouling)
Capacity (permeate flux):
High pore density
Thinness (thin active layer, i.e. low resistance for solvent
permeation)
Hydrophilicity in water filtration
High selectivity: Narrow pore size distribution
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Membrane Classification

Membrane
Classification

Materials Structure Etc. Applications

Mixed
Organic Inorganic Symmetric Asymmetric Based on
Matrix
Driving Force
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Membrane Generations
First generation membrane processes
Microfiltration (MF)
Ultrafiltration (UF)
Nanofiltration (NF)
Hyper filtration (HF) /Reverse osmosis (RO)
Electro dialysis (ED)
Second generation membrane processes
Gas separation (GS)
Pervaporation (PV)
Membrane Distillation (MD)
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Filtration Spectrum
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Typical Specification of Pressure Driven Membrane

Processes
Best Separation Technique:
1. Technical Feasibility
2. Economical Feasibility

Hydraulic
Membrane Size Pressure Permeability
MWCO (Da)
Processes (nm) (bar) (L.m-2.hr-1. bar-
1)

Microfiltration >100 0.1 - 2 > 106 >1000

(MF)
Ultrafiltration (UF) 100-2 1-10 5000- 10-1000
300,000
Nanofiltration 10-2 3-20 200-1000 1.5-30
(NF)
Reverse Osmosis <2 10-80 <200 0.05-1.5
(RO)
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Microfiltration (MF)
Separates suspended solids and some colloidal materials
(>0.1m) from a feed stream.
The concentrate requires periodic removal or cleaning to
prevent the eventual plugging of membrane feed passage
ways.
Two common forms:
crossflow filtration: a fluid stream runs parallel to a
membrane
dead-end (perpendicular) filtration : all of the fluid passes
through the membrane, and all of the particles that cannot
fit through the pores of the membrane are stopped.
http://www.edinformatics.com/math_science/suspensions_colloids.htm
http://www.800mainstreet.com/9/0009-001-mix-solut.html
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Ultrafiltration (UF)
Ultrafiltration this is the size exclusion based pressure driven
membrane separation process range of 2-100 nm.
Typical rejected species or constituents includes sugar,
biomolecules, polymers, colloidal particles, emulsified oils, micro
biological materials, and high molecular weight organic substances
depending upon their molecular weight, molecular size and also
shape.
Typically not effective at separating organic streams
These membrane are classified according to their molecular weight
cut off (MWCO),which is usually defined as smallest molecular weight
species for which membranes have more than 90% rejection.
Different available configuration of UF membrane are:
i. Flat membrane in plate and frame structure
ii. Tubular
iii. Spirally wounded module (most commonly used)
iv. Hollow fiber type
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Nanofiltration (NF) Loose RO

NF is used when low molecular weight solutes such as inorganic
salts/small organic molecules (glucose, sucrose) have to be
separated.
The organic compounds bearing very low molecular weight linear
chain structure are rejected while monovalent cations combined with
monovalent anions to form compound or salts pass through the
permeate.
The divalent cations or anions do not pass though the permeate. This
property of rejection due to ionic charges is made use in the softening
of water for the various applications.
The molecular weight cut for such types of membranes is lower than
that of UF membrane.
Applications of Nanofiltration
1. Heavy metals are rejected preferentially by Nanofiltration membrane.
2. Dye factories effluent contains highly concentrated dye, salts and some
acids. Nanofiltration can very effectively separate the dye and concentrate
it to. This way of concentration and purification reduces the loss for dye
thereby effecting a reduction in ETP load.
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Reverse Osmosis
Essentially a pressure driven membrane diffusion process
for separating dissolved solutes.
Smallest pore structure, 5-15 A0 (0.5 nm - 1.5 nm), that
they are within the range of thermal motion of the polymer
chains that form the membrane.
The accepted mechanism of transport through these
membranes is called the solution-diffusion model.
allows only the smallest organic molecules and
unchanged solutes to pass through the semi-permeable
membrane along with the water
>95-99% of inorganic salts and charged organics will
also be rejected by the membrane due to charge
repulsion established at the membrane surface
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Electrodialysis (ED)

https://www.gewater.com/products/electrodialysis-reversal-water-treatment
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Electrodialysis (ED)
In the ED process a semi-permeable barrier allows passage of
either positively charged ions (cations) or negatively charged
ions (anions) while excluding passage of ions of the opposite
charge. These semi-permeable barriers are commonly known
as ion-exchange, ion-selective or electrodialysis membranes.
The principle of electrodialysis process is that, the arrangement
consists of a series of anion and cation exchange membranes
arranged in an alternating pattern between an anode and a
cathode. The cation pass easily through the negatively charged
anion exchange membrane.
The overall result is an ion concentration increase in alternate
components, while other components simultaneously become
depleted of ions.
Ion exchange membrane should have a high selectivity for
appositively charged ions and a high ion permeability.
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Gas Separation
Separation of gases is due to their different solubility and
diffusivity in the polymer membranes.
Rate of permeation:
Proportional to pressure differential across the membrane,
solubility of gas in the membrane, and diffusivity of gas
through membrane.
Inversely proportional to the membrane thickness.
Pore size: < 1 nm.
Applications:
The generation of N2 from air. The production of oxygen from
air is also significant.
The recovery of hydrogen from refinery off-gases (CO, N2, C1,
C2) and vapors (C3+, CO2), i.e. Palladium membranes
The removal of carbon dioxide from natural gas.
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Membrane Distillation
Air/vapour
2 6
Feed Permeate
H2O H2O
1
T1 T2 5

Hydrophobic
Liquid water porous membrane Liquid water 3

T1>T2

Fractionation by membrane distillation, 1, porous hydrophobic membrane polymer;

2, feed; 3, vapour space; 4, cooling water; 5, chilled wall; 6, condensed droplets.
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Membrane Distillation
It is a process in which two liquid or solutions at different temperatures are
separated by a porous hydrophobic membrane.
It is a type of low temperature, reduced pressure distillation.
It is one of the membrane processes in which the membrane is not directly
involved in separation the only function of the membrane is to act as a barrier
between the twos phases. Selectivity is completely determined by the vapor
liquid equilibrium involves. This means that the component with the highest
partial pressure will show the highest permeation rate.
Such transport occur in a sequence of three steps:
Evaporation on the high-temperature side.
Transport of vapor molecules through the pores of the hydrophobic porous
membrane.
Condensation on the low-temperature side.
The liquid/solution must not wet the membrane otherwise the pores will be
filled for capillary force.
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Membrane Distillation

Comparison between Conventional Distillation and Membrane

Distillation
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Pervaporation
Pervaporation is the combination of two words perm selective and
evaporation. It is used for separation of miscible liquids.
In pervaporation, a liquid mixture contacts one side of a membrane,
and the permeate is removed as a vapor from the other.
The driving force for the process is the low vapor pressure on the
permeate side of the membrane generated by cooling and
condensing the permeate vapor.
The attraction of pervaporation is that the separation obtained is
proportional to the rate of permeation of the components of the liquid
mixture through the selective membrane. Therefore, pervaporation
offers the possibility of separating closely boiling mixtures or
azeotropes that are difficult to separate by distillation or other means.
Differs from all other membrane processes because of the phase
change of the permeate.
http://pervaporation-membranes.com/home/introduction-to-pervaporation-and-vapor-
permeation/
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Pervaporation
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Pervaporation
Three steps sequence:
Sorption of permeating components at the feed side into the
membrane.
Transport of components across the membrane by diffusion
according to Ficks law.
Desorption at the permeate side into vapor phase under
vacuum.

Applications:
The main industrial application of pervaporation is the dehydration of
organic solvents, in particular, the dehydration of 9095 % ethanol
solutions, a difficult separation problem because of the ethanolwater
azeotrope at 95 % ethanol.
It is used for the removal of volatile organic compounds (VOCs).
Removal of organics from water.
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Dialysis
Dialysis is membrane processes that use pressure difference as
the driving force.
It is of great importance in hemodialysis, in which urea, uric acid,
phosphate and chlorides are removed from blood without
removing essential higher molecular weight compounds and blood
cells. This dialysis is called as artificial kidney.
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Dialysis
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Membrane Bio Reactor (MBR)

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Membrane Bio Reactor (MBR)

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Membrane Applications
Process
Reverse Desalination (seawater and brackish water), production of ultra-pure water,
osmosis production of high purity water (boiler feed, electronics, medical,
pharmaceutical), Removal of all salts and small organic molecules.
Nanofiltration Water softening, desalination of brackish water, wastewater treatment,
retention of dyes (textile industry), fractionation in sugar industry, Removal of
multivalent salts and small organic molecules
Ultrafiltration Concentration of emulsions, concentration of protein, biotech separations,
membrane bioreactors, filtration of beer, wine and milk, oil-water emulsions
separation, pharmaceutical products separation (enzymes and antibiotics),
prefiltration in water treatment
Microfiltration Potable water production (removal of colloids and bacteria), mineral
processing, enhanced contacting (ion exchange, activated carbon),
Prefiltration in water treatment, screening of bacteria
Electrodialysis Desalination, treatment of saline effluent (water recycling), concentration of
seawater for inorganic salt recovery, effluent treatment from galvanizing
processes, recovery of lactic acid from diary effluents, removal of acid from
fruit juice.
Pervaporation Alternative to azeotropic distillation, dehydration of ethanol, separation of
chlorinated hydrocarbon from organic solvents, separation of hydrocarbon
mixtures
Gas permeation Ammonia synthesis, methanol synthesis, synthesis gas, natural gas, refinery
gas, uranium isotope separation.
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Membrane 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.
Clean technology with operational ease
No additives are required
Continuous separation
No Complex instrumentation
Greater design flexibility in designing systems and easy
up-scaling
Membrane processes can easily be combined with other
separation processes
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Membrane Disadvantages
High cost. Membranes (and associated systems) are
costly
Low fluxes. The permeate flowrate available are still too
low for some applications
Generally low selectivity
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.
Biofouling/membrane fouling
Low membrane lifetime
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Membrane Applications
 50

Future Developments
Development and Advancement of materials for effective
membrane strength and separations

Overcoming the problem of Membrane Fouling

To design membranes for high selectivity

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Comprehensive Videos
Lecture Series (1-5):
https://www.youtube.com/channel/UCtdqcNHhhBTxNmfNd-PYXzw

RO membrane for Desalination and Solvent Resistant

Nanofiltration:
http://www.icam-
online.org/research/lectureseries/membranesforseparatingmolecules/